RESUMO
A rhodium catalyzed direct regioselective oxidative annulation by double C-H activation is described to synthesize highly substituted quinolones from pyridones. The reaction proceeds at mild conditions with broad scope and wide functional group tolerance. These novel quinolones were explored to recognize nitroaromatic compounds.
RESUMO
Conjugated polymers (CPs) that show stable and reversible cation insertion/deinsertion under ambient conditions hold great potential for optoelectronic and energy storage devices. However, n-doped CPs are prone to parasitic reactions upon exposure to moisture or oxygen. This study reports a new family of napthalenediimide (NDI) based conjugated polymers capable of undergoing electrochemical n-type doping in ambient air. By functionalizing the NDI-NDI repeating unit with alternating triethylene glycol and octadecyl side chains, the polymer backbone shows stable electrochemical doping at ambient conditions. We systematically investigate the extent of volumetric doping involving monovalent cations of varying size (Li+, Na+, tetraethylammonium (TEA+)) with electrochemical methods, including cyclic voltammetry, differential pulse voltammetry, spectroelectrochemistry, and electrochemical impedance spectroscopy. We observed that introducing hydrophilic side chains on the polymer backbone improves the local dielectric environment of the backbones and lowers the energetic barrier for ion insertion. Surprisingly, when using Na+ electrolyte, the polymer films exhibit higher volumetric doping efficiency, faster-switching kinetics, higher optical contrast, and selective multielectrochromism when compared to Li+ or TEA+ electrolytes. Using well-tempered metadynamics, we characterize the free energetics of side chain-ion interactions to find that Li+ binds more tightly to the glycolated NDI moieties than Na+, hindering Li+ ion transport, switching kinetics, and limiting the films' doping efficiency.
RESUMO
A water-soluble dilithium salt BODIPY derivative (LiBDP) with appended dicarboxylate pseudo-crown ether [NO4] coordinating sites has been designed, synthesized and characterized successfully for the selective and sensitive recognition of Cd2+ in aqueous media. The chemosensor exhibits a remarkable increase in fluorescence intensity as well as a distinct color change upon the addition of Cd2+ over other environmentally and biologically relevant metal ions in H2O. The fluorometric response of LiBDP is attributed to the metal chelation-enhanced fluorescence (MCHEF) effect which has been confirmed by a strong association constant of 2.57 ± 1.06 × 105 M-1 and Job's plot, indicating 1 : 1 binding stoichiometry between LiBDP and Cd2+. Frontier molecular orbital analysis (obtained from DFT studies) also illustrates the turn-on fluorescence of the probe by blocking photoinduced electron transfer (PET) after coordination to Cd2+. The probe can detect Cd2+ in a competitive environment up to a submicromolar level in a biologically significant pH range. The sensor is proved to be reversible and reusable by the alternative addition of Cd2+ followed by S2-. The OFF/ON/OFF sensing behavior is utilized to construct an INHIBIT molecular logic gate based on the two inputs of Cd2+ and S2- and a fluorescence intensity at 512 nm as an output. The test paper experiment demonstrates the practical utility of LiBDP to monitor Cd2+ in an aqueous sample. Finally, the sensing probe was utilized to monitor Cd2+ in living cells.
RESUMO
Organometallic molecular wires with π-conjugation along their molecular backbones are of considerable interest for application in molecular-scale electronics. In this regard, thienylethynyl-based π-conjugated oligomers of three, five and seven thienylethynyl units with -C[triple bond, length as m-dash]C-H termini have been successfully synthesized through stepwise Pd(0)/Cu(i)-catalyzed Sonogashira coupling. The corresponding highly soluble diruthenium(ii) diacetylide complexes (O1-Ru2, O3-Ru2, O5-Ru2 and O7-Ru2, respectively) have been prepared by the reaction of cis-Ru(dppe)2Cl2 and NaPF6 in DCM with the corresponding rigid rod-like thienylethynyl oligomers with one, three, five and seven thienylethynyl π-conjugated segments containing alkynyl termini (O1, O3, O5 and O7). These Ru(ii)-Cl capped diacetylide complexes have been further functionalized by incorporating a phenylacetynyl moiety to afford [Ru(ii)-C[triple bond, length as m-dash]C-Ph]-capped diacetylide organometallic wires (O1-Ru2-Ph, O3-Ru2-Ph, O5-Ru2-Ph and O7-Ru2-Ph). The photophysical properties of the highly soluble thienylethynyl-based oligomers and Ru(ii)-organometallic wires have been explored to understand their electronic properties. Electrochemical studies of the binuclear ruthenium(ii)-alkynyl complexes showed highly interesting results, revealing long-range electrochemical communication between the two remote Ru(ii) termini connected even with five and seven thienylethynyl units. DFT computational studies further support the long range electrochemical communication between the redox active metal termini through heavy participation of the thienylethynyl bridge in the corresponding mono-oxidized mixed valence species of the organometallic wire-like complexes.